Higher aliphatic alcohols



more May 13,1941

v manna ALIPHATIO ALoonoLS. Wilhelm Normann, Chemnits, Germany;

administrate-ix Nonnnnn,

deceased, assignor to American ration, Wilmington, Del., a

Martha I of Wilhelm Nonnann,

Hyalool incoorlloration ct Dela- No Drawing. Application February. 10,1933, serial No. 656,197. In Germany January 27, 1930' 3 Clalrll- (CI.The higher aliphatic alcohols heretofore were made by reducing theesters of the corresponding organic acids by means of sodium and loweraliphatic alcohols. This process is however relav tively expensive andlittle suited for use on a large commercial scale.

It has now been found that the higher aliphatic alcohols, say from eightatoms of carbon upward, may be obtained smoothly and in good yield fromthe corresponding fatty acid esters, by, catalytic reduction by means ofhydrogen upon working in accordance with certain conditions. Finelydivided metallic copper which may be deposited on a suitable carrier,for example, kiesele guhr, is used as the catalyst. If hydrogen be-260-638) 100-200 atmospheres and at a temperature of about 350 C. Thenormal primary alcohol CrzHzsOH (lauric alcohol) is. obtained with asmoothly proceeding reaction resulting in a very goodyield. It-is alsopossible to use, instead of the ethyl I ester of lauric acid, the estermixture which recaused to act on the fatty acid ester to be reduced, at300-400 0., in the presence of the copper catalystandunder a pressure of100-200 atmospheres, thecorresponding alcohol will be obtained in a verygood yield. Alcohols in a somewhat lesser yield may be obtained bycarrying out the reactions at lower or higher temperatures end/orpressure, for example, at other temperatures within the range oi about200 to 450 C. or other pressures within the range of about 60 to 500atmospheres.

The unexpected fact has now been discovered that other Mown catalyticmetals, for example, nickel, platinum and palladium, at the preferredtemperature and pressure conditions stated, produce a further reductionto the hydrocarbon stage, so that only very little alcohol is obtained.Though the copper catalyst is preferred tor the production or alcohols,hydrogenating catalysts in general may be used with at least some degreeoi success, examples of the same being the metals, tin, cadmium, silver,and/or their omdes and the omdes of zinc, chromium, magiurn andmanganese. shows the specific set that it catalyzes only the first stepoi the reduction process, namely the conversion of the ester into thealcohol, but not the awn. so that it become of the t reduction stepnearly quantitatively. The itant invention is independent of the met bywhich the contact between the ester, hydrogen and catalyst is obtainedso long as the temperature and pressure conditions disclosed areemployed. The contact between the catalyst and the ester may be effectedby ordinary mixing, or the ester may be flowed past the catalyst held ina stationary position.

Example in a closed reaction vessel, a pressure oi about Thus, metalliccopper suits upon esteriiying all the fatty acids of cocoanut fat withethyl alcohol or some other lower aliphatic alcohol. when the mixture orethyl esters is employed, the traction boiling between 255 and 275 C. isused. The. esters 0! other higher fatty acids with univalent alcohols,as

well as the corresponding glycerin esters may also be processed in ananalogous way. Thus'the conversion of the naturally occurring fatty acidglycerids into other esters may be eliminated and the mixturesotglycerids or individual glycerids isolated therefrom may be subjected tothe reduction in the manner described.

The products obtained may be used for 111 commercial purposes, forexample in the various branches oi the art of textile improvement, andmay be employed without further refining or separation, They are inparticular excellently suitable for making suliurized products, because,even if they do not contain of alcohols,

'yet they do contain nearly 100% of suliurizable constituents, which mayinclude also the admixed unsaturated compounds.

This application is a continuationin part of applicant's co-pendingapplication, Serial No. 510,326, filed January 21, 1931.

' Having thus described the invention, .what is claimed as new anddesired to be secured by Letters Patent is:

l. The process for the production of alcohols of high molecular weightwhich comprises passing a glyceride of a carboxylic -acid having morethan 8 carbon atoms in the acid radical with hydrogen, while heating toa temperature of the range from 200 to 400 (3., over a copper containinghydrogenation catalyst.

'2. The process for the catalytic hydrogenation of glyceride ofaliphatic alkyl mono-carboxylic acids having more than 8 carbon atoms inthe acid radical which comprises passing vapors of the said esterstogether with hydrogen, while heating to a temperature of the range from200 to 400" C., over a copper containing hydrogenation catalyst.

3; The process of preparing higher aliphatic alcohols having at leasteight carbon atoms comprising treating a glyceride of an aliphatic acidhaving more than eight carbon atoms with hydrogen in the presence of ametallic copper catalyst at a temperature in excess of 200 C, and undersuperatmospheric pressure.

4. The process for the production oi alcohols 0! high molecular weightwhich comprises passing a glyceride of a carboxylic acid having morethan 8 carbon atoms in the acid radical with hydrogen while heating to atemperature of the range from 200 to 400 C. over a metallic coppercatalyst.

5. The process of preparing higher aliphatic alcohols from thecorresponding glycerides having more than 8 carbon atoms in the acidradical comprising reacting a mixture of such a glyceride and hydrogenat a temperature in excess of 200 C. under a superatmospheric pressurein the presence of a copper containing hydrogenating catalyst.

6. The process of reducing glycerides of higher aliphatic acids intotheir corresponding higher aliphatic alcohols comprising reacting such aglyceride with hydrogen at a temperature of from 300 to 400 C. under apressure of from 100 to 200 atmospheres in thepresence of a coppercatalyst.

7. The process of producing alcohols in very good yields throughtreatment carried out in the liquid phase, which comprises mixing aglyceride of a. carboxylic acid, the number of carbon atoms in said acidbeing greater thanthe number of carboxyl groups, said glyceride being ina liquid state with a copper containing hydrogenation catalyst andcontacting hydrogen with said mixture at a temperature of from 200 to400 C. and under superatmospheric pressure.

8. The process of preparing higher aliphatic alcohols from naturallyoccurring glycerides containing fatty acid radicals of at least 8 carbonatoms comprising reacting such naturally occurring fatty acid glyceridesand hydrogen at a temperature below 400 C. under a superatmosphericpressure in the presence of a copper containing hydrogenating catalyst.

WILHELM NORMANN.

